Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/068—Microemulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
  • A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
  • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
  • A61K8/731—Cellulose; Quaternized cellulose derivatives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties
  • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/59—Mixtures
  • A61K2800/596—Mixtures of surface active compounds

Definitions

• This invention relates to conditioning shampoo compositions containing a specific surfactant component comprising an ethoxylated alkyl sulfate surfactant havmg from about 1 to about 8 moles of ethoxylation and an amphoteric surfactant in a shampoo with insoluble, dispersed, nonionic conditioning agent, a low viscosity organic conditioning oil and a select soluble cellulosic cationic organic polymer hair conditioning agent
• the compositions provide improved hair conditioning performance, including improved wet hair feel.
• the hair can also suffer from a loss of "softness” perceived by the user upon drying.
• the hair can also suffer from increased levels of static upon drying after shampooing. This can interfere with combing and can result in fly-away hair.
• a variety of approaches have been developed to alleviate the after-shampoo problems. These range from the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses Hair rinses are generally liquid in nature and must be applied in a separate step following the shampooing, left on the hair for a length of time, and rinsed with fresh water. This, of course, is time consuming and is not as convenient as shampoos containing both cleanmg and hair conditioning ingredients.
• Cationic conditioning agents are highly desirable for use in hair conditioning due to their abilities to control static, improve wet detangling, and provide a silky wet hair feel to the user.
• One problem which has been encountered in shampoos relates to compatibility problems between good cleanmg anionic surfactants and the many conventional cationic agents which historically have been used as conditioning agents. Efforts have been made to minimize adverse interaction through the use of alternate surfactants and improved cationic conditioning agents.
• Cationic surfactants which provide good overall conditioning in hair rinse products in general, tend to complex with anionic cleaning surfactants and provide poor conditioning in a shampoo context.
• soluble cationic surfactants that form soluble ionic complexes do not deposit well on the hair.
• Soluble cationic surfactants that form insoluble ionic complexes deposit on the hair but do not provide good hair conditioning benefits, and tend to cause the hair to have a dirty, coated feel.
• insoluble cationic surfactants e.g., tricetyl methyl ammonium chloride
• Many cationic polymers tend to build up on the hair to result in an undesirable, "unclean" coated feel.
• Cationic polymers therefore, conventionally, are preferably used at limited levels to minimize this problem. This, however, can limit the overall conditioning benefits that are obtained.
• cationic conditioning agents commonly do not provide optimal overall conditioning benefits, particularly in the area of "softness", especially when delivered as an ingredient in a shampoo composition.
• Materials which can provide increased softness are nonionic silicones. Silicones in shampoo compositions have been disclosed in a number of different publications. Such publications include U.S. Patent 2,826,551, Geen, issued March 1 1 , 1958; U.S. Patent 3,964,500, Drakoff, issued June 22, 1976; U.S. Patent 4,364,837, Pader, issued December 21, 1982; and British Patent 849,433, Woolston, issued September 28, 1960. While these patents disclose silicone containing compositions, they also did not provide a totally satisfactory product in that it was difficult to maintain the silicone well dispersed and suspended in the product.
• HEI 1 [1987]- 168612 Horie et al., discloses detergent compositions containing cationic surfactant and/or cationic polymer, anionic surfactant, and specific esters of the formula RCOOR' wherein R and R' are straight or branched chain alkyls.
• EPO Patent Application Publication No. 0413 417 discloses shampoo containing anionic surfactant, and conditioning agents such as insoluble silicone (preferably aminosilicone), cationic surfactant, polyethylenes, paraffins, microcrystalline waxes, C j g ⁇ fj fatty acids or triglycerides, high fatty alcohol esters of high fatty acids, and beeswax.
• conditioning agents such as insoluble silicone (preferably aminosilicone), cationic surfactant, polyethylenes, paraffins, microcrystalline waxes, C j g ⁇ fj fatty acids or triglycerides, high fatty alcohol esters of high fatty acids, and beeswax.
• Another patent document which discloses shampoo compositions and a variety of conditioning agents is U.S. Patent 3,964,500, Drakoff, issued June 22, 1976. This patent relates to shampoo containing silicone conditioner and a hair bodying agent selected from certain wood rosins, shellac, sucrose acetate isobutyrate
• composition disclosed combines a surfactant system (selected from anionic, nonionic, or amphoteric, or mixtures thereoO, cationic guar derived polymer, and nonvolatile silicone having particle size less than 2 microns.
• a surfactant system selected from anionic, nonionic, or amphoteric, or mixtures thereoO, cationic guar derived polymer, and nonvolatile silicone having particle size less than 2 microns.
• Applicants have found that by utilizing a select cationic cellulose derived polymer in place of the cationic guar derived polymer in a specific surfactant system, which optimizes the conditioning coacervate formed, the present invention results in significantly improved conditioning performance.
• compositions can provide improved conditioning while reducing the level of undesirable side effects that can result from increasing the level of conditioning agent in prior known conditioning systems.
• a conditioning agent system containing too much silicone can result in silicone build up on the hair over repeated usages and to loss of fullness of the hair. Too much oil results in an oily feel and a loss of fullness of the hair. Too much cationic conditioning agent results in a coated, dirty feel of the hair.
• the components of the present invention can provide improved overall conditioning while minimizing the adverse effects of conditioning agent build-up that otherwise can be incurred upon increasing the levels of individual components in prior known conditioning systems. It has now been found that by adding a low viscosity organic conditioning oil increases the deposition of, e.g., silicone conditioners, and provides improved conditioning benefits such as wet and dry feel and combing.
• the present invention is directed to hair conditioning shampoo compositions comprising: a) from about 5.0% to about 50% of a surfactant component comprising: i) an ethoxylated alkyl sulfate surfactant having from about 1 to about 8 moles of ethoxylation; and ii)an amphoteric surfactant; b) from about 0.01% to about 3.0% of a cationic cellulosic polymer having a molecular weight of from about 400,000 to about 1 ,500,000 and charge density of from about 0.6 to about 3 meq/g.; c) from about 0.005% to about 5% of a water insoluble non-volatile conditioning agent having an average particle size below about 4 microns; d) from about 0.05% to about 5%, by weight, of an organic, nonvolatile, water insoluble liquid which is solubilized in the surfactant component and having a viscosity of from about 1 to about 300 centipoise selected from
• the shampoo compositions of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well any of the additional or optional ingredients, components, or limitations described herein. All percentages, parts and ratios are based upon the total weight of the shampoo compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.
• the term “soluble” refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1 % by weight of the material in water at 25°C.
• the term “insoluble” refers to all other materials that are therefore not sufficently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% by weight of the other material in water at 25°C.
• liquid refers to any visibly (by the naked eye) flowable fluid under ambient conditions (about 1 atmosphere of pressure at about 25°C)
• the shampoo compositions of the present invention comprise from about 5.0% to about 50% of a detersive surfactant component comprising: i) an ethoxylated alkyl sulfate surfactant having from about 1 to about 8 moles of ethoxylation; and ii) an amphoteric surfactant component to provide cleaning performance to the composition and wherein said the resulting composition comprises less than about 5%, preferably less than about 3% and most preferably less than about 2% of alkyl sulfate ethoxylated surfactant having less than 1 mole of ethoxylation
• the detersive surfactant component can optionally comprises additional detersive surfactants.
• Such surfactants should be physically and chemically compatible with the essential components described herein, or should not otherwise unduly impair product stability, aesthetics or performance.
• Concentration of the surfactant component in the shampoo composition ranges from about 5% to about 50%, preferably from about 8% to about 30%, more preferably from about 10% to about 25%, even more preferably from about 12% to about 20%, by weight of the composition.
• the alkyl ether sulfates have the formula: RO(C2H4 ⁇ ) x S ⁇ 3M, wherein R is alkyl or alkenyl of from about 8 to about 24 carbon atoms, x is 1 to 8, and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium.
• the cation M, of the anionic detersive surfactant should be chosen such that the detersive surfactant component is water soluble. Solubility will depend upon the particular anionic detersive surfactants and cations chosen.
• R has from about 8 to about 18 carbon atoms, more preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon atoms in both the alkyl and alkyl ether sulfates.
• the alkyl ether sulfates are typically made as condensation products of ethylene oxide and mono ⁇ hydric alcohols having from about 8 to about 24 carbon atoms.
• the alcohols can be derived from fats, e.g., coconut oil, palm kernal or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil or palm kemal are preferred herein.
• Such alcohols are reacted with between about 1 and about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
• Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
• Suitable amphoteric surfactant components for use in the shampoo composition herein include those which are known for use in shampoo compositions or other personal care cleansing composition, and which contain a group that is anionic at the pH of the shampoo composition. Concentration of such surfactant components in the shampoo composition preferably ranges from about 0.5 % to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 5% by weight of the composition. Examples of amphoteric surfactants suitable for use in the shampoo compostion herein are described in U.S. Patents 5, 104,646 (Bolich Jr. et al.), U.S. Patent 5, 106,609 (Bolich Jr. et al.), which descriptions are inco ⁇ orated herein by reference.
• amphoteric detersive surfactants which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
• an anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
• Examples of compounds falling within this definition are sodium 3-dodecyi-aminopropionate, sodium 3- dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, N- higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and
• MIRANOL the products sold under the trade name "MIRANOL" and described in U.S. Patent 2,528,378.
• amphoterics sometimes classified as zwitterionics, such as betaines can also useful in the present invention.
• Such zwitterionics are considered as amphoterics in the present invention where the zwitterionic has an attached group that is anionic at the pH of the composition.
• betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, and lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine.
• high alkyl betaines such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarbox
• the sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines and amidosulfobetaines, wherein the RCONH(CH ) radical is attached to the
• T e shampoo compositions of the present invention may further comprise additional detersive surfactants for use in combination with the anionic detersive surfactant component described hereinbefore.
• Suitable optional surfactants include nonionic surfactants, cationic surfactants, and combinations thereof. Any such surfactant known in the art for use in hair or personal care products may be used, provided that the optional additional surfactant is also chemically and physically compatible with the essential components of the shampoo composition, or does not otherwise unduly impair product performance, aesthetics or stability. Concentration of the optional additional surfactants in the shampoo composition may vary with the cleaning or lather perfo ⁇ nance desired, the optional surfactant selected, the desired product concentration, the presence of other components in the composition, and other factors well Icnown in the art.
• optional anionic detersive surfactants which can be used in addition to the alkyl ether sulfates are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [ R1-SO3-M ] where Rj is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation, as previously described, subject to the same limitations regarding polyvalent metal cations as previously discussed.
• detersive surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods, including bleaching and hydrolysis.
• a sulfonating agent e.g., SO3, H2SO4
• alkali metal and ammonium sulfonated C ] ⁇ -i O n-paraffins are preferred.
• anionic detersive surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil or palm kernal oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil or palm kemal oil.
• Other similar anionic surfactants are described in U.S. Patent 2,486,921 ; U.S. Patent 2,486,922; and U.S. Patent 2,396,278, which descriptions are incorporated herein by reference.
• anionic detersive surfactants suitable for use in the shampoo compositions are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium
• N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinnate diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
• suitable anionic detersive surfactants include olefin sulfonates having about 10 to about 24 carbon atoms.
• olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
• the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SOo, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
• the alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 10 to about 24 carbon atoms, preferably about 12 to about 16 carbon atoms. Preferably, they are straight chain olefins.
• the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
• Another class of anionic detersive surfactants suitable for use in the shampoo compositions are the beta-alkyloxy alkane sulfonates. These compounds have the following formula:
• R ⁇ is a straight chain alkyl group having from about 6 to about 20 carbon atoms
• R ⁇ is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms
• M is a water-soluble cation as hereinbefore described.
• Preferred additional anionic detersive surfactants for use in the shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate
• Cationic Hair Conditioning Polymer Cationic cellulosic derivative polymer materials suitable for use herein include those of the formula:
• A is a cellulose anhydroglucose residual
• R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof
• R 1 , R-, and R ⁇ independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in Rl, R ⁇ and R ⁇ ) preferably being about 20 or less
• X is an anionic counterion, as previously described.
• the cationic cellulosic polymer has a molecular weight ranging from about 400,000 to about 1 ,500,000, preferably from about 500,000 to about 1,500,000 and most preferably from about 800,000 to about 1,200,000 and a charge density of from about 0.6 to about 3 meq./gr, preferably from about 0.7 to about 2.0 meq/gr. and most preferably from about 0.9 to about 1.5 meq/gr.
• Cationic cellulose is available from Amerchol Co ⁇ . (Edison, NJ, USA) in their Polymer JR and LR series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10.
• the water soluble cationic described herein are either soluble in the shampoo composition, or preferably are soluble in a complex coacervate phase in the shampoo composition formed by the cationic polymer and the anionic surfactant described hereinbefore.
• Complex coacervates of the cationic polymer can also be formed with other optional anionic components of the shampoo composition.
• Coacervate formation is dependent upon a variety of criteria such as molecular weight, component concentration, and ratio of interacting ionic components, ionic strength (including modification of ionic strength, for example, by addition of salts), charge density of the cationic and anionic components, pH, and temperature.
• ionic strength including modification of ionic strength, for example, by addition of salts
• charge density of the cationic and anionic components pH, and temperature.
• Coacervate systems and the effect of these parameters have been described, for example, by J. Caelles, et al., "Anionic and Cationic Compounds in Mixed Systems", Cosmetics & Toiletries, Vol. 106, April 1991, pp 49-54, C. J. van Oss, "Coacervation, Complex-Coacervation and Fiocculation", J. Dispersion Science and Technology, Vol.
• the cationic polymer it is believed to be particularly advantageous for the cationic polymer to be present in the shampoo composition in a coacervate phase, or to form a coacervate phase upon application or rinsing of the shampoo to or from the hair.
• Complex coacervates are believed to more readily deposit on the hair.
• the cationic polymer exist in the shampoo composition as a coacervate phase or form a coacervate phase upon dilution. If not already a coacervate in the shampoo composition, the cationic polymer will preferably exist in a complex coacervate form in the shampoo upon dilution with water.
• the shampoo compositions of the present invention further comprises an insoluble hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations generally range from about 0.005% to about 5%, preferably from about 0.05% to about 4%, more preferably from about 0.1 % to about 3.5%, most preferably from about 0.2% to about 3%, by weight of the shampoo compositions.
• the insoluble hair conditioning particles useful in the present invention have a particle size range below about 4 microns, preferably below about 1 micron, most preferably below about 0.5 microns.
• Useful conditioning agents include silicone and petrolatum. Silicone Hair Conditioning Agent
• non-volatile silicone conditioning agents Most preferred for use herein are non-volatile silicone conditioning agents. Typically it will be intermixed in the shampoo composition so as to be in the form of a separate, discontinuous phase of dispersed, insoluble particles, also referred to as droplets. These droplets may be suspended with a suspending agent described hereinafter.
• the silicone hair conditioning agent phase will comprise a silicone fluid hair conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enhance silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones).
• nonvolatile refers to silicone material with little or no significant vapor pressure under ambient conditions, as is understood by those in the art. Boiling point under one atmosphere (atm) will preferably be at least about 250°C, more preferably at least about 275°C, most preferably at least about 300°C. Vapor pressure is preferably about 0.2mm HG at 25°C or less, preferably about 0.1mm HG at 25°C or less.
• the silicone hair conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or mixtures thereof. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.
• the silicone hair conditioning agents for use in the shampoo compositions preferably have a viscosity of from about 20 to about 2,000,000 centistokes, more preferably from about 1,000 to about 1,800,000 centistokes, even more preferably from about 10,000 to about 1,500,000 centistokes, most preferably from about 30,000 to about 1 ,000,000 centistokes, at 25°C.
• the viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Co ing Co ⁇ orate Test Method CTM0004, July 20, 1970.
• Optional silicone fluid for use in the shampoo compositions includes silicone oil which are flowable silicone materials with a viscosity of less than 1 ,000,000 centistokes, preferably between about 5 and 1 ,000,000 centistokes, more preferably between about 10 and about 600,000 centistokes, more preferably between about 10 and about 500,000 centistokes, most preferably between 10 and 300,000 centistokes at 25°C.
• Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
• Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used.
• Optional Silicone oils for use in the composition include polyalkyl or polyaryl siloxanes which conform to following formula:
• R is aliphatic, preferably alkyl or alkenyl, or aryl
• R can be substituted or unsubstituted
• x is an integer from 1 to about 8,000.
• Suitable unsubstituted R groups include alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups.
• Suitable R groups also include cationic amines and quaternary ammonium groups.
• the aliphatic or aryl groups substituted on the siloxane chain may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the shampoo compositions, are chemically stable under normal use and storage conditions, are insoluble in the shampoo compositions, and are capable of being deposited on and, of conditioning, the hair.
• the two R groups on the silicon atom of each monomeric silicone unit may represent the same group or different groups. Preferably, the two R groups represent the same group.
• Preferred alkyl and alkenyl substituents are C 1 -C5 alkyls and alkenyls, more preferably from C ⁇ - C4, most preferably from C1 -C2.
• the aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups can be straight or branched chains and preferably have from one to five carbon atoms, more preferably from one to four carbon atoms, even more preferably from one to three carbon atoms, most preferably from one to two carbon atoms.
• the R substituents hereof can also contain amino functionalities, e.g.
• alkamino groups which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri- alkylamino and alkoxyamino groups wherein the aliphatic portion chain length is preferably as described above.
• the R substituents can also be substituted with other groups, such as halogens (e.g. chloride, fluoride, and bromide), halogenated aliphatic or aryl groups, and hydroxy (e.g. hydroxy substituted aliphatic groups).
• Suitable halogenated R groups could include, for example, tri-halogenated (preferably fluoro) alkyl groups such as -R ! -C(F)3, wherein R* is C 1 -C3 alkyl
• polysiloxanes include polymethyl -3,3 3 trifluoropropylsiloxane
• Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl
• the pre ⁇ ferred silicones are polydimethyl siloxane, polydiethyisiloxane, and polymethylphenylsiloxane Polydimethylsiloxane is especially preferred
• Other suitable R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy
• the three R groups on the end caps of the silicone may also represent the same or different groups
• nonvolatile polyalkylsiloxane fluids that may be used include, for example, polydunethylsiloxanes These siloxanes are available, for example, from the General Electric Company in their Viscasil R and SF 96 series, and from Dow Commg in their Dow Commg 200 series
• polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Commg as 556 Cosmetic Grade Fluid
• polyether siloxane copolymers that may be used mclude, for example, a polypropylene oxide modified polydimethylsiloxane (e g , Dow Commg DC- 1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
• ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof
• Suitable alkylamino substituted silicones include those conforming to the following formula
• Suitable cationic silicone fluids include those conforming to the formula described hereinabove.
• R 2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a saturated hydrocarbon radical, preferably an alkyl radical containing from 1 to 20 carbon atoms, and A * denotes a halide ion.
• silicone cationic polymers which can be used in the shampoo compositions are those which conform to the following formula:
• R- denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably an alkyl or alkenyl radical such as methyl
• R4 denotes a hydrocarbon radical, preferably a C j -Ci alkylene radical or a C j -C j , and more preferably C j -Cg, alkyleneoxy radical
• Q is a halide ion, preferably chloride
• r denotes an average statistical value from 2 to 20, preferably from 2 to 8
• s denotes an average statistical value from 20 to 200, and preferably from 20 to 50.
• a preferred polymer of this class is available from Union Carbide under the name "UCAR SILICONE ALE 56.”
• silicone fluids for use in the silicone conditioning agents are insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent 4,152,416; Noll and Walter, Chemistrv and Technology of Silicones, New York: Academic Press 1968; and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are inco ⁇ orated herein by reference.
• the silicone gums will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000.000, specific examples of which include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.
• the silicone hair conditioning agent can also comprise a mixture of polydimethylsiloxane gum (viscosity greater than about 1,000,000 centistokes) and polydimethylsiloxane oil (viscosity from about 10 to about 100,000 centistokes), wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.
• nonvolatile, insoluble silicone fluid conditioning agents are high refractive index silicones, having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55. Although not intended to necessarily be limiting, the refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60.
• Polysiloxane "fluid" includes oils as well as gums.
• the high refractive index polysiloxane fluid suitable for purposes hereof includes those conforming to the formula described hereinabove, as well as cyclic polysiloxanes such as those conforming to the following formula:
• n is from about 3 to about 7, preferably from 3 to 5.
• the high refractive index polysiloxane fluids contain a sufficient amount of aryl-containing R substituents to increase the refractive index to the desired level, which is described above.
• R and n must be selected so that the material is nonvolatile, as defined above.
• Aryl-containing substituents contain alicyclic and heterocyclic five and six membered aryl rings, and substituents containing fused five or six membered rings.
• the aryl rings themselves can be substituted or unsubstituted.
• Substituents include aliphatic substituents, and can also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, etc.
• aryl-containing groups include substituted and unsubstituted arenes, such as phenyl, and phenyl derivatives such as phenyls with C -C alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes (e.g. phenyl C 6 -C . alkynes).
• Heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc.
• Fused aryl ring substituents include, for example, napthalene, coumarin, and purine.
• the high refractive index polysiloxane fluids will have a degree of aryl-containing substituents of at least about 15%, preferably at least about 20%, more preferably at least about 25%. even more preferably at least about 35%, most preferably at least about 50%.
• the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%.
• polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution.
• the polysiloxane fluids hereof will have a surface tension of at least
• Preferred high refractive index polysiloxane fluids have a combination of phenyl or phenyl derivative substituents (preferably phenyl), with alkyl substituents, preferably C 1-C4 alkyl (most preferably methyl), hydroxy, C1-C4 alkylamino (especially -R'NHR ⁇ NH2 where each R and R independently is a C.-C. alkyl, alkenyl, and/or alkoxy.
• High refractive index polysiloxanes are available from Dow Coming Co ⁇ oration (Midland, Michigan, U.S.A.) Huls America (Piscataway, New Jersey, U.S.A.), and General Electric Silicones (Waterford, New York, U.S.A.).
• the spreading agent will preferably reduce the surface tension by at least about 2 dynes/cm " ,
• 2 proportions present in the final product is preferably 30 dynes/cm or less, more preferably about 28
• the surface tension will be in the range of from about 15 to about 30, more typically from about 18 to about 28, and most generally from
• the weight ratio of the highly aryiated polysiloxane fluid to the spreading agent will, in general, be between about 1000: 1 and about 1 : 1, preferably between about 100: 1 and about 2: 1, more preferably between about 50: 1 and about 2: 1, most preferably from about 25: 1 to about 2: 1.
• fluorinated surfactants particularly high polysiloxane: spreading agent ratios may be effective due to the efficiency of these surfactants.
• ratios significantly above 1000: 1 may be used.
• References disclosing examples of some suitable silicone fluids for use in the shampoo compositions include U.S. Patent 2,826,551 , U.S. Patent 3,964,500, U.S.
• Silicone resins can be included in the silicone conditioning agent. These resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the inco ⁇ oration of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin.
• silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins.
• the ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material.
• Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein.
• the ratio of oxygen:silicon atoms is at least about 1.2: 1.0.
• Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosiianes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized.
• Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved foim in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and inco ⁇ orated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.
• Silicone materials and silicone resins in particular can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone.
• M denotes the monofunctional unit (C ⁇ SiO 5; D denotes the difunctional unit (C ⁇ SiO; T denotes the trifunctional unit (CH3)SiO j 5; and Q denotes the quadri- or tetra-functional unit Si0 2 .
• Primes of the unit symbols, e.g., M', D', T, and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc.
• the molar ratios of the various units either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereoO or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system.
• Higher relative molar amounts of T, Q, T and or Q' to D, D', M and/or M' in a silicone resin is indicative of higher levels of crosslinking.
• the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.
• the silicone resins for use herein which are preferred are MQ, MT, MTQ, MDT and MDTQ resins.
• the preferred silicone substituent is methyl.
• MQ resins wherein the M:Q ratio is from about 0.5: 1.0 to about 1.5: 1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.
• the weight ratio of the nonvolatile silicone fluid, having refractive index below 1.46, to the silicone resin component, when used, is preferably from about 4:1 to about 400: 1, preferably this ratio is from about 9: 1 to about 200: 1, more preferably from about 19: 1 to about 100: 1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above.
• the silicone resin forms a part of the same phase in the compositions hereof as the silicone fluid, i.e. the conditioning active, the sum of the fluid and resin should be included in determining the level of silicone conditioning agent in the composition.
• the shampoo composition of the present invention may further comprise a suspending agent for the insoluble conditioning agent.
• suspending agents are well known in the shampoo and conditioning art. Examples of some suitable suspending agents are described in U.S. Patent 4,741,855, U.S. Patent 4,788,006, U.S. Patent 4,704,272, U.S. Patent 2,798,053, which descriptions are inco ⁇ orated herein by reference.
• Suitable suspending agents for use in combination with the insoluble conditioning agent include acyl derivatives, long chain amine oxides, xantham gum, and carboxyvinyl polymers.
• suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl ether copolymer.
• water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydorxe
• the shampoo compositions of the present invention comprise a low viscosity, organic conditioning oil which is solubilized in the surfactant component as an additional hair conditioning agent for use in combination with the cationic hair conditioning polymer described hereinbefore.
• concentration of the low viscosity, organic oil ranges from about 0.05% to about 3%, preferably from about 0.08% to about 1.5%, more preferably from about 0.1% to about 1%, by weight of the shampoo composition.
• the low viscosity, organic, conditioning oils are water insoluble, water dispersible, liquids selected from the group consisting of hydrocarbon oils and fatty esters, or combinations thereof , wherein the organic conditioning oil has a viscosity of from about 1 to about 300 centipoise, preferably from about 1 to about 150 centipoise, more preferably from about 2 to about 50 centipoise, as measured at 40°C according to ASTM D-445.
• these low viscosity organic conditioning oils provide the shampoo composition with improved conditioning performance when used in combination with the essential components of the composition.
• These organic conditioning oils are believed to be solubilized in the surfactant micelles of the shampoo composition. It is also believed that this solubilization into the surfactant micelles contributes to the improved hair conditioning performance of the shampoo compositions herein.
• Suitable organic conditioning oils for use in the shampoo composition include hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), including polymers thereof.
• Hydrocarbon oils preferably contain from about 12 to about 19 carbon atoms.
• Branched chain hydrocarbon oils, including hydrocarbon polymers, can and typically will contain more than 19 carbon atoms.
• hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, poiybutene, polydecene, and combinations thereof.
• Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons can also be used, examples of which include highly branched, saturated or unsaturated, alkanes such as the permethyl-substituted isomers, e.g., the permethyl-substituted isomers of hexadecane and eicosane, such as 2, 2, 4, 4, 6, 6, 8, 8-dimethyl- 10-methylundecane and 2, 2, 4, 4, 6, 6-dimethyl-8-methylnonane, sold by Permethyl Co ⁇ oration.
• Hydrocarbon polymers such as poiybutene and polydecene, especially poiybutene, can also be used.
• organic conditioning oils for use in the shampoo composition include a liquid polyolefin such as a liquid polyalphaolefin or a hydrogenated liquid polyalphaolefin.
• Polyolefins for use in the shampoo composition herein are prepared by polymerization of olefenic monomers containing from about 4 to about 14 carbon atoms, preferably from about 6 to about 12 carbon atoms.
• Polyalphaolefins are preferred, and are prepared by polymerization of 1 -alkene monomers having from about 4 to about 14 carbon atoms, preferably from about 6 to about 12 carbon atoms
• Non limiting examples of olefenic monomers for use in preparing the polyolefin liquids herein include ethylene, propylene, 1 -butene, 1 -pentene, 1-hexene, 1 -octene, 1 -decene, 1-dodecene, 1- tetradecene, branched chain isomers such as 4-methyl- 1 -pentene, and combinations thereof.
• olefin-containing refinery feedstocks or effluents are also suitable for preparing the polyolefin liquids.
• olefin-containing refinery feedstocks or effluents Preferred, however, are the hydrogenated alpha-olefin monomers having from about 4 to about 14 carbon atoms, or combinations thereof, examples of which include 1-hexene to 1-hexadecenes and comb ations thereof, and preferably are 1 -octene to 1 -tetradecene or combinations thereof Water
• the shampoo compositions of the present invention comprise from about 20% to about 94%, preferably from about 50% to about 94%, more preferably from about 60% to about 85%, by weight of water.
• the shampoo compositions of the present mvention may further comprise one or more optional components known for use in shampoo or conditioning compositions, provided that the optional components are physically and chemically compatible with the essential component described herein, or do not otherwise unduly impair product stability, aesthetics or performance.
• Optional components typically range from about 0.001% to about 10% by weight of the shampoo compositions
• Optional components mclude anti static agents, dyes, organic solvents or diluents, pearlescent aids, foam boosters, additional surfactants or cosurfactants (nonionic, cationic, zwitte ⁇ onic), pediculocides, pH adjusting agents, perfumes, preservatives, protems, skm active agents, suspending agents, styling polymers, sunscreens, thickeners, vitamins, and viscosity adjusting agents
• This list of optional components is not meant to be exclusive, and other optional components can be used.
• the shampoo compositions of the present mvention can be prepared by usmg various formulation and mixing techniques or methods known in the art for preparing surfactant or conditioning compositions, or other similar compositions.
• the shampoo compositions of the present invention are used in a conventional manner for cleansing and conditioning hair or skin.
• An effective amount of the composition for cleansing and conditioning the hair or skm is applied to the hair or skin, that has preferably been wetted with water, and then rinsed off.
• Such effective amounts generally range from about I g to about 50g, preferably from about lg to about 20g.
• Application to the hair typically includes working the composition through the hair such that most or all of the hair is contacted with the composition
• This method for cleansing and conditioning the hair comprises the steps of: a) welting the hair with water, b) applying an effective amount of the shampoo composition to the hair, and c) rinsing the shampoo composition from the hair using water. These steps can be repeated as many times as desired to achieve the desired cleansing and conditioning benefit. Examples
• compositions can be prepared by conventional formulation and mixing techniques.
• Component amounts are listed as weight percents and exclude minor materials such as diluents, filler, and so forth.
• the listed formulations therefore, comprise the listed components and any minor materials associated with such components.
• Polyquatemium- 10 (3) 0.15 0.15 0.30 0.10 0.10
• Dimethicone is an emulsion of 60.000 csk polydimethyl siloxane with p article size of approximately 300 nm available from Dow Corning (DC 1664).
• Carbopol 981 is a crosslinked polyacrylate available from B F. Goodrich
• Polyquatemium- 10 is UCare Polymer JR30M from Amerchol.
• Poiybutene is Indopol L-14 from Amoco.

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